Fungicidal substituted ureidophenyl thioureas

ABSTRACT

Ureidophenyl thioureas of the formula:   in which EACH INDEPENDENTLY STANDS FOR A HALOGEN ATOM, ALKYL WITH 1-4 CARBON ATOMS OR ALKOXY WITH 1-4 CARBON ATOMS, N STANDS FOR 0, 1 OR 2, R stands for alkyl with 1-12 carbon atoms, R&#39;&#39; and R&#39;&#39;&#39;&#39; each stands independently for a hydrogen atom or alkyl with 1-4 carbon atoms, and R&#39;&#39;&#39;&#39;&#39;&#39; stands for a hydrogen atom, alkyl with 1 or 2 carbon atoms (which may carry at least one substituent selected from halogen, cyano, alkoxy with up to 4 carbon atoms and alkoxycarbonyl with up to 5 carbon atoms), alkyl with 3 to 18 carbon atoms (which carries at least one substituent selected from halogen, cyano, alkoxy with up to 4 carbon atoms and alkoxycarbonyl with up to 5 carbon atoms), cycloalkyl with 5 to 8 ring carbon atoms, aralkyl (the aryl moiety of which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), phenyl (which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), acyl with up to 18 carbon atoms (which may be substituted by halogen and/or lower alkyl), aroyl (which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), alkylsulfonyl with up to 18 carbon atoms, arylsulfonyl (which may carry at least one substituent selected from halogen, amino, lower alkyl and lower alkoxy) or dialkylamino with up to 4 carbon atoms, possess fungicidal properties.

[ Nov. 18, 1975 1 FUNGICIDAL SUBSTITUTED UREIDOPHENYL THIOUREAS [75] Inventors: Arno Widdig, Blecher; Engelbert Ki'ihle, Bergisch Gladbach; Klaus Sasse, Schildgen; Hans Scheinpflug, Leverkusen; Ferdinand Grewe, Burscheid; Helmut Kaspers; Paul-Ernst Frohberger, both of Leverkusen, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: .Sept. 21, 1973 [21] Appl. No.: 399,653

Related US. Application Data [62] Division of Ser. No. 89,500, Nov. 13, 1970, Pat. No.

[30] Foreign Application Priority Data Nov. 29, 1969 Germany 1960029 [52] US. Cl. 424/300 [51] Int. Cl? A01N 9/12 [58] Field of Search 424/300; 260/270 [56] References Cited UNITED STATES PATENTS 3,780,089 12/1973 Widdig et a1. 260/470 FOREIGN PATENTS OR APPLICATIONS 4,519,078 3/1970 Japan 260/470 1,054,777 4/1959 Germany 260/470 1,191,406 5/1920 United Kingdom 260/470 694,362 l/l970 South Africa 260/470 Primary Examiner-Albert T. Meyers Assistant Examiner-Leonard Schenkman Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT Ureidophenyl thioureas of the formula:

NH 0 NH COOR R 11 in which each X independently stands for a halogen atom, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms,

n stands for 0, l or 2,

R stands for alkyl with l-l2 carbon atoms,

R and R" each stands independently for a hydrogen atom or alkyl with l-4 carbon atoms, and

R stands for a hydrogen atom, alkyl with l or 2 carbon atoms (which may carry at least one substituent selected from halogen, cyano, alkoxy with up to 4 carbon atoms and alkoxycarbonyl with up to 5 carbon atoms), alkyl with 3 to 18 carbon atoms (which carries at least one substituent selected from halogen, cyano, alkoxy with up to 4 carbon atoms and alkoxycarbonyl with up to 5 carbon atoms), cycloalkyl with 5 to 8 ring carbon atoms, aralkyl (the aryl moiety of which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), phenyl (which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), acyl with up to 18 carbon atoms (which may be substituted by halogen and/or lower alkyl), aroyl (which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), alkylsulfonyl with up to 18 carbon atoms, arylsulfonyl (which may carry at least one substituent selected from halogen, amino, lower alkyl and lower alkoxy) or dialkylamino with up to 4 carbon atoms, possess fungicidal properties.

9 Claims, No Drawings FUNGICIDAL SUBSTITUTED UREIDOPHENYL THIOUREAS This is a division of application Ser. No. 89,500, filed Nov. 13, 1970 now US. Pat. No. 3,780,089.

The present invention relates to and has for its objects the provision of particular new ureidophenyl thioureas, which possess fungicidal properties, active comin which each X independently stands for a halogen atom, alkyl with 1-4 carbon atoms or alkoxy with 1 carbon atoms,

n stands for 0, 1 or 2,

R stands for alkyl with 1-12 carbon atoms,

R and R" each stands independently for a hydrogen atom or alkyl with 1-4 carbon atoms and,

R' stands for a hydrogen atom, alkyl with l or 2 carbon atoms (which may carry at least one substituent selected from halogen, cyano, alkoxy with up to 4 carbon atoms and alkoxycarbonyl with up to 5 carbon atoms), alkyl with 3 to 18 carbon atoms (which carries at least one substituent selected.

from halogen, cyano, alkoxy with up to 4 carbon atoms and alkoxycarbonyl with up to 5 carbon atoms), cycloalkyl with 5 to 8 ring carbon atoms, aralkyl (the aryl moiety of which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), phenyl (which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), acyl with up to 18 carbon atoms (which may be substituted by halogen and- /or lower alkyl), aroyl (which may carry at least one substituent selected from halogen, lower alkyl and lower alkoxy), alkylsulfonyl with up to 18 carbon atoms, arylsulfonyl (which may carry at least one substituent selected from halogen, amino, lower alkyl and lower alkoxy) or dialkylamino with up to 4 carbon atoms. The compounds of the formula (I) have been found to exhibit strong fungicidal properties.

The invention also provides a process for the production of the ureidophenylthioureas of the formula (1) in which a 2-ureidoaniline derivative of the formula in which X, n, R, R, and -R" have the meanings stated above, is reacted with an isothiocyanate of the formula S=C=NCOOR (111) in which R has the meaning stated above, I in the presence of a diluent (which term herein includes a solvent).

It is surprising that the ureidophenylthioureas of the formula (1) exhibit a higher fungicidal activity than zinc ethylene-l,Z-bis-dithiocarbamate. The active compounds according to the invention therefore represent an enrichment of the art.

When N-2-aminophenyl-N'-methylurea and ethoxy carbonylisothiocyanate are used as starting materials, the reaction course can be represented by the following equation:

The Z-ureidoaniline derivatives used as starting materials are defined by the formula,(ll). In this formula, as

in formula (I), X stands preferably for chlorine, bromine, fluorine, methyl, ethyl, isopropyl, n-butyl, methoxy, ethoxy or isopropoxy; n stands preferably for the numbers 0 or 1; R and R" stand preferably for hydrogen, methyl or ethyl, R stands preferably for hydrogen, alkyl with 1 or 2 carbon atoms, substituted alkyl with l to 12 carbon atoms, benzyl, phenyl, p-tolyl, pmethoxyphenyl, methoxyethyl, ethoxylpropyl, cyanopentyl, acetyl, benzoyl, methanesulfonyl, p-toluenesulfonyl or dimethylamino.

As examples of the 2-ureidoaniline derivatives, there may be mentioned: 2-amino-phenylurea, N-2- aminophenyl-N'-methylurea, N-Z-aminophenyl-N', N'- dimethylurea, N-2-aminophenyl-N-O-cyanopentylurea, N-2-aminophenyl-N-2-methoxyethylurea, N-2- aJninophenyl-N'-benzylurea, N-2-aminophenyl-N'- phenylurea, N-Z-aminophenyl-N-acetylurea, N-2- aminophenyl-N'-benzoylurea, N-2-aminophenyl-N-ptoluenesulfonylurea, 4- 2-aminophen yl 1 l -dimethylsemicarbazide, and the like.

The 2-ureido-anilines used as starting materials are partially known (see Beilsteins Handbuch der organischen Chemie, Volume 13, pages 20-32, Berlin, 1930; Volume 13, l. Ergaenzungswerk (1st Supplement), pages 8-10, Berlin, 1933; Volume 13, 2. Ergaenzungswerk (2nd Supplement), pages 14-23, Berlin-Goettingen-Heidelberg, 1950). They may also be obtained by reduction or catalytic hydrogenation of the appropriate 2-nitrophenylureas.

The isothiocyanates used as starting materials are defined by the formula (III), in which, as in formula (I), R stands preferably for methyl, ethyl or propyl. Some of the isothiocyanates are known [see J. Chem. Soc. 93, 696( l908)]; they can also be obtained from the reaction between alkali metal isothiocyanates and haloformic acid esters. Suitable isothiocyanates include methoxycarbonylisothiocyanate, ethoxycarbonylisothiocyanate and propoxycarbonylisothiocyanate.

As diluents, when carrying out the process according to the invention all inert organic solvents are suitable. These include for example hydrocarbons, such as benzine, ligroin, hexane, benzene and toluene chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methylisopropyl ketone, acetophenone and cyclohexanone; and any desired mixtures of the said solvents.

The reaction temperature can be varied within a fairly wide range. In general, the work is carried out at from substantially between l to 60C, preferably from between about 0 to 40C.

When carrying out the process according to the invention, 1 mole of isothiocyanate is preferably used per mole of the Z-ureidoaniline derivative. Amounts greater or lesser by up to are possible without sub- ;tantial diminution of the yield. When the reaction mix- :ure is cooled, the end products are obtained in crystaline form and can be separated by suction filtration 1nd, optionally, purified by redissolving or recrystalliration. A preferred embodiment of the process com- )rises preparing the isothiocyanate in an inert solvent 1nd reacting it directly, without further isolation, with he o-phenylenediamine derivative.

The active compounds according to the invention ex iibit a strong fungitoxic activity. In the concentrations iecessary for the control of fungi, they do not damage :ultivated plants, and have a low toxicity to warm- )looded animals. For these reasons, they are suitable as :rop protection agents for the control of fungi. Fungioxic agents in crop protection are used for the control )f Archimycetes, Phycomycetes, Ascomycetes, Basidi- )mycetes and Fungi imperfecti.

The active compounds according to the invention lave a very broad activity spectrum and can be applied .gainst parasitic fungi which infect above-the-soil parts |f plants or attack the plants from the soil, as well as gainst seed-borne pathogenic agents.

They are particularly effective against fungi which ause powdery mildew diseases. To this group of fungi aere belong predominantly representatives from the irsiphaceae family with the moxt important genera eing Erysiphe, Uncinula (Oidium), Sphaerotheca and 'odosphaera. Important fungi include Ersyip/ze cihoracearunz, Podosp/zaera leuc'otriclza and Uncinula nerlmr.

Theactive compounds according to the invention lso give good results in the control of rice diseases. hus, they show an. excellent activity against the fungi iricularia oryzae and Pellicularia sasakii, by reason f which theyicanbe'used'for the joint control of aese two diseases. This means a substantial adance, since, up to now, agents of different chemical onstitution were required against these two funi. urprisingly, the active compounds show not only a rotectiveactivity, but also a curative and systemic ffect.

The compounds according to the invention, however, also act against other fungi which infect rice or other cultivated plants, such as Coc/zliobolus myiabeanus, Mvcosp/zaerella musicola, Cercaspora personate, Barrytis cinerea, Alternaria species, Verticillium alboatrum, P/zialop/zora c'inerescens and Fusarium species, as well as against bacterium Xant/zemonas oryzae.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc. halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as convenional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as nonionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other fungicides, or herbicides, insecticides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0. l%, and

cation or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.000ll%, preferably 0.01-1%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally about 0.000l-95%, and preferably 0.0l-95%, by weight of the mixture.

In the case of use as seed dressings, applied amounts of 0.1 to g, preferably 0.2 to 2g, of active compound per kg of seed are suitable.

In the case of use as soil-treatment agents, applied amounts of l to 500 g, preferably 10 to 200 g per cubic meter of soil are usually necessary.

The active compounds according to the invention also show an insecticidal and acaricidal activity as well as an activity against some mold fungi and yeasts. In concentration higher than those necessary for fungicidal activity, the substances inhibit plant growth.

The active compound can also be used in accordance with the well-known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effectiv atomizing equipment, in finely divided form, e.g. average particle diameter of from -100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about or by weight of the active compound, or even the active substance alone, e.g. about 20-100% by weight of the active compound.

In particular, the present invention contemplates methods of selectively killing, combating or controlling fungi, which comprises applying to at least one of (a) such fungi and (b) their habitat, i.e. the locus to be pro tected, a fungicidallyfeffective or toxic amount of thc particular active compound of the invention alone 0: together with a carrier vehicle as noted above. The in stant formulations or compositions are applied in the usual manner, for instance by squirting, spraying atom izin'g, vaporizing, scattering, dusting, fumigation, watering, sprinkling, pouring, dressing, incrustations, anc the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture EXAMPLE 1 Erysiphe test Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol ether Water: 950 parts by weight f The amount of the active compound required for the desired concentration of active compound in the spray liquid is mixed with the stated amount of the solvent, and the concentrate is diluted with the stated amount of water containing the stated additions.

Young cucumber plants :with about threefoliage leaves are sprayed with the spray liquid until dripping wet. The cucumber plants remain in a greenhouse for 24 hours to dry. They are then, for the purpose of inoculation, dusted with conidia of the fungus Er \'siphe ciclzoracearum. The plants are subsequently placed in a greenhouse at 2324C and at a relative atmospheric humidity of about 75%. I

After 12 days, the infection ofthe cucumber plants is determined as a percentage of the untreated but also inoculated control plants. 0% means no infection; 100% that the infection is exactly as great as in the case of the control plants. I a

The active compounds, the concentrations of the active compounds and the results obtained canbe seen from the following Table 1.

Table 1 Active compound (known) Table l-continued infection as a percentage of the infection of the untreated control with a concentration of active compound EXAMPLE 2 Piricularia and Pellicularia Test Solvent: 4 parts by weight acetone Dispersing agent: 0.05 parts by weight sodium oleate Water: 95.75 parts by weight Other additives: 0.2 parts by weight gelatin plants is then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Piricularia oryzae and placed in a chamber at 24 26C and relative atmospheric humidity. The other batch of the plants is infected with a culture of Pellicularia sasakii grown on malt agar and placed at 28 30C and 100% relative atmopsheric humidity.

5 to 8 days after inoculation, the infection of all the leaves present at the time of inoculation with Piricularia oryzae is determined as a percentage of the untreated but also inoculated control plants. In the case of the plants infected with PeIIicuIaria sasakii, the infection on the leaf sheaths after the same time is also determined in proportion to the untreated but infected control. 0% means no infection; 100% means that the infection is exactly as great in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table 2.

Table 2 Piricularia (a) and Pellicularia (b) Test pr. protective cur. curative lnfection as a percentage of the infection of the Active compound untreated control with a concentration of active compound (in 71) of NH-COOC H pr. 0 25 CH cover of a layer of muslin and 2 cm of moderately moist EXAMPLE 3 compost soil, is exposed to optimum germination con- Seed dressing test/bunt of wheat ditions for the spores for 10 days at lO C in a refrigera- (seed-bom mycosis) tor.

To produce a suitable dry dressing, the active com- 60 The germination of the spores on the wheat grains, pound is extended with a mixture of equal parts by each of which is contaminated with about 100,000

weight of talc and kieselguhr to give a finely powdered spores, is subsequently determined microscopically.

mixture with the desired concentration of the active The smaller the number of spores which have germicompound. nated, the more effective is the active compound.

Wheat seed is contaminated with 5 g of the chlamy- 65 The active compounds, the concentrations of the acdospores of Tilletia cariespe kg of seed; To apply the tive compounds in the dressing, the amounts of dress dressing, the seed is shaken with the-dressing in a 1 .ing used and the percentage spore germination can be closed glass flask. The seed, on moist loam under a seen from the following Table 3: i

Table 3 Seed dressing test/bunt of wheat Active compound Concentration Amount of Spore Mycellium growth test 20 parts by weight agar-agar (powdered) 3O pans by weight malt extract 950 parts by weight distilled water Proportion of solvent to nutrient substrate: 2 parts by weight acetone 100 parts by weight agar nutrient substrate Nutrient substrate used:

a diameter of 9 cm. Control plates without admixture of the preparation are also set up.

When the nutrient substrate is cold and solid, the plates are inoculated with the species of fungi stated in the Table and incubated at about 21C.

Evaluation takes place after 4-10 days, according to the speed of growth of the fungi. In the evaluation, the radial growth of mycelium on the treated nutrient substrates is compared with the growth on the control nutrient substrate. The evaluation is effected with the following index numbers:

Ono growth of fungus 1very strong inhibition of growth 2-moderate inhibition of growth 3 slight inhibition of growth 4growth equal to untreated control 13 The active compounds, concentrations of active compounds and the results obtained can be seen from the following Table 4:

I of the testfungi.

been sterilized and then inoculated with pure culture The soilis'filled into 5 pots, each of which is sow:

Table 4 Mycelium growth test FUNGl Concentration of Verti- Phialoactive 'Pellicillium phora C erco- 3 Piricucompound cularia albocinerspora laria Active compound in ppm sasakii atrum escens musae oryzae CH NH-CSS (A) Zn l0 4 3 4 3 4 CH NHCSS (known) Ti NHCNHCOOC H lO 0 2 0 0 NHlCl--NHCH t NHCNHCOOC H (6) 1o 0 0 0 0 NHCNHCH CH- OCH3 T1 Nl l-C-NH-COOC H (1) l0 0 0 0- to NHCNH-CH;;

i m c w-comm (2) r I .10 l oo "NHCNH'N I H CH --"Niig -c'" isiiicooczns (3) w-l-c- Nucnni-c -l m a l o o ii U131 p; I

NH-C-NHQCOOCQH; I l0 0, ()5 0 -'N,a -N.u@ O

- EXAMPLE 5 Soil treating agent test/soil-bome mycoses To produce a suitable preparation of the active compound, the active compound is extended with talc to a content of 5% and subsequently with'quartz sand to content of 0.5% of active compound.

The preparation of the active compound is uniformly mixed with Fruhstorfer standard soil, which has first Table Soil treating agent test/soil-bprne m ycoses Active compound Concentration Test fungi:

of active F usarium compound culmorum, mg/liter soil Host plant: Pea Temperature range: 22-25 Fruhstorfer standard soil. sterilized untreated I 9O Fruhstorfer standard soil. sterilized and inoculated untreated 5 H NHCSS (A) i n 100 2 H NH-CSS (known) i NHCNH COOC H l) NHfiNH-CH=, I00

NH -NHCOOC H 2) E J: CH 100 NH-C-NH-N l I CH NHC-NHCOOC H I00 20 3) NH fiNH (C 2)sCN EXAMPLE 6 with 20 cc of the liquid to be used for watering, in the stated concentration of active compound with reference to 100 cc of soil;

y p test/systemic The plants so treated are, after'the treatment, inocuolvent: 4.7 parts by weight acetone lated With conidia 0f the fungus Erysiphe Cl mulsifie Parts t choracearum. The plants are subsequently placed in a later: parts by weight The amount of the active compound required for the esired concentration in the liquid to be used for waterig is mixed with the stated amount of the solvent, and

greenhouse at 2324C and at a relative atmospheric humidity of 70%. 1

After 12 days, the infection of the cucumber plants is determined as a percentage of the untreated but also inoculated control plants. 0% means no infection;

ie concentrate is diluted with the stated amount of 50 means that the mfecnon ls exactly as great as m ater containing the stated additions. Cucumber plants grown in standard soil are, in the neto two-leaf stage, watered three times in one week the case of the control plants.

The active compounds, the concentrations of the active compounds and the results obtainedcan be seen from the following Table 6:

Table 6 v Active compound (known) Table 6-continued lnfection as a percentage of the infection of the untreated control with a concentration of active compound of [20 ppm fi NHC-NH-COOC H,-, (6) O NHfiNH-CH CH OCH ISI NHCNHCOOC H O NHfiNHCH- O i NHCNHCOOC H (2) CH 0 NHCNH-N H 3 0 ISI NH-CNHCOOC H (3) l3 NHICiNH-(CH2)5CN EXAMPLE 7 Podosphaera test (powdery mildew of apples) [Protective] Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol ether Water: 95 parts by weight main in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of They are then inoculated by dusting with conidia of the apple powdery mildew causative organism (Podosphaera leucotricha Salm.) and placed in a greenhouse at a temperature of 21 23C and at a relative atmospheric humidity of about 70%.

Ten days after the inoculation, the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants.

0% means no infestation; means that the infestation is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table 7:

Table 7 Active compound Podosphaera test/Protective vInfection as a percentage of the infection of the untreated control with a concentration of active compound of Dispersing agent: 0.3 parts by weight alkylaryl polyglycol Table 7-continued H-C NH-CHB Apple seedlings grown in standard soil are, in the 3 EXAMPLE 8 4 leaf stage, watered once in one week with cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to 100 cc of soil. The plants so treated are, after the treatment, inether I oculated with conidia of Podosphaera leucotricha Salm Podosphaera test (systemic) Solvent: 4.7 parts by weight acetone 95 Parts by weigh and placed in a greenhouse at a temperature of 21 I 23C and at a relative atmospheric humidity of about The amount f active c d i d f th 1 10 days after the inoculation, the infection of the sired concentration of the active compound in the liq- Seedlings S ermined as a percentage of the unuid to be used for watering is mixed with the stated treated b so noculated Control plants. amount of solvent, and the concentrate is diluted with 0% means r10 infection; means a the fecthe stated amount of water which contains the stated 50 tiOh is exactly 88 great as in the Case of the Control additions. plants.

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table 8:

Table 8 Podosphaera test/Systemic Active compound Infection as a percentage of the infection of the untreated control with a concentration of active compound of ppm S (known) Table 8-continued Podosphaera test/Systemic Active compound Infection as a percentage of the infection of the untreated control with a concentration of active compound-of 120 ppm NH-C-NH-CH I EXAMPLE 9 Fusicladium test (apple scab) f l her at 18 20C and at an atmospheric humidity l 100%. The plants are then placed in a greenhou: where they dry.

After standing for a suitable period of time, the plan Solvent: 4] parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyg Water: 95 parts by weight are sprayed dripping wet with the spray liquid prepare lycol ether 1n the manner described above. The plants are subs The amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of 'solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.

Young apple seedlings in the 4 6 leaf stage are inoculated with an aqueous conidium suspension of the apple scab causative organism Fusicladium dendriticum el and incubated for 18 hours in a humidity cham- EXAMPLE l Fusicladium test (systemic) lvent: 4.7 parts by weight acetone lulsifier: 0.3 parts by weight alkylaryl polyglycol ether iter: 95 parts by weight The amount of active compound required for the deed concentration of the active compound in the liql to be used for watering is mixed with the stated iount of solvent, and the concentrate is diluted with 2 stated amount of water which contains the stated ditions.

Apple seedlings grown in standard soil are, in the 3 eaf stage, watered once in one week with cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to cc of soil. The plants so treated are, after the treatment, inoculated with an aqueous conidium suspension of F usicladium dendriticum el and incubated for 18 hours in a humidity chamber at 18 20C and at a relative atmospheric humidity of 100%. The plants are subsequently placed in a greenhouse for 14 days. 7

15 days after inoculation, the infection of the seedlings is determined as a percentage of the untreated but also inoculated control plants. 0% means no infection; 100% means that the infection is exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table l0:

Table 10 Fusicladium test/systemic Infection as a percentage of the infection of the untreated control with a concentration of active Active compound compound of 120 ppm S ll It will be realized by the artisan that all of the foregong compounds contemplated by the present invention aossess the desired strong fungicidal properties, with regard to a broad spectrum of activity, as well as a comaaratively low toxicity toward warm-blooded creatures and a concomitantly low phytotoxicity, enabling such :ompounds to be used with correspondingly favorable :ompatibility with respect to warm-blooded creatures and plants for more effective control and/or elimina- :ion of fungi by application of such compounds to such fungi and/or their habitat.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and :hanges may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A fungicidal composition comprising a fungicidally effective amount of a ureidophenyl thiourea of the formula in which R stands for alkyl with 1-12 carbon atoms, R and R each stands independently for a hydrogen or alkyl with l-4 carbon atoms, and R stands for alkyl with 1 or 2 carbon atoms; alkyl with 1 to 12 carbon atoms substituted by alkoxy with 1 to 4 carbon atoms, cyano, dialkylamino with up to 4 carbon atoms; phenyl; benzyl; p-tolyl; p methoxyphenyl; acetyl; benzoyl; methanesulfonyl; or p-toluenesulfonyl, and a diluent. 2. The composition of claim 1 wherein the compound is selected from the group consisting of:

N-[2-(phenylureido)-phenyl]-N-ethoxycarbonylthiourea, N-[ 2-( benzylureido )-phenyl ]-N '-ethoxycarbonyl-thiourea, N-[ 2-( methoxyethylu reido)-pheny1]-N '-ethoxycarbonylthiourea, N-[2-(methylureido)-phenyl]-N-ethoxycarbonylthiourea, N-[ 2-dimethylaminou reido -phenyl -N -ethoxycarbonyl-thiourea, and N-[Z-(cyanopentylureido)-phenyl]-N-ethoxycarbonyl-thiourea. 3. A method of combating fungi which comprises applying to said fungi or their habitat a fungicidally effective amount of a ureidophenyl thiourea of the formula:

5. The method of claim 3 wherein the compound is N-[2-( benzylureido )-phenyl ]-N -ethoxycarbonyl-thiourea of the formula 29 30 6- The method of Claim 3 wherein the Compound is 8. The method of claim 3 wherein the compound is -(rnethoxyethylure1d0 )-p y h y N-[Z-(dimethylaminoureido )-phenyl -N'-ethoxycarbonylthlourea of the formula V b ylthi f the formula 5 s s Q ll NH NHCOOC2H5 7 /NH-- NHCOOC2H,-, 6 Q CH3 1 \NH-CNH-CH2CH2O-CH;,. 10 NH-(T-NH-N I 7. The method of claim 3 wherein the compound is The method of Claim 3 wherein the Compound is N-[ 2-( methylureido )-phenyl]-N'-ethoxycarbonyl-thil5 N[2( cyanpemylureid Hhenyl "ethoxycarbo' ourea of the formula nyl-thlourea of the formula PATENT NO.

DATED UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION 3,920,831 November 18, 1975 Page 1 of 2 INVENTOR(S) Arno Widdig et al v It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col.

Col.

Col.

3, line 65 13, Table 4 21, Table 8,

22, Table 9,

25, Table 10,

25, Table 10,

correct spelling of "fungi".

. (3) cancel final "CH" and substitute CN Compound (2) insert bonds Compound (5) after "NH-" insert Compound (2) insert bonds CH as follows: N I CH3 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,920,831 Page 2 of 2 DATED November 18,1975

|NVENT0R(5) Arno Widdig et a1 It is certified that error appears in the above-identified patent and that said Letters Patent 6 are hereby corrected as shown below:

"NH C01. 25, 11ne-65, v Example 11, before (Compound 5) Qt lnsert Same compound, after "NH-" insert c 1 27 1' o lne 30, a Compound (2) insert bonds 3 as follows: N O r 3 Signed and Scalcdthis Twenty-fourth Day of August 1976 [SEAL] Arrest:

I RUTH czmsou a c. MARSHALL'DANN I Arresting Officer Commissioneroflatems and Trademarks 

1. A FUNGICIDAL COMPOSITION COMPRISING A FUNGICIDALLY EFFECTIVE AMOUNT OF A UREIDOPHENYL THIOUREA OF THE FORMULA
 2. The composition of claim 1 wherein the compound is selected from the group consisting of: N-(2-(phenylureido)-phenyl)-N''-ethoxycarbonyl-thiourea, N-(2-(benzylureido)-phenyl)-N''-ethoxycarbonyl-thiourea, N-(2-(methoxyethylureido)-phenyl)-N''-ethoxycarbonylthiourea, N-(2-(methylureido)-phenyl)-N''-ethoxycarbonyl-thiourea, N-(2-dimethylaminoureido)-phenyl)-N''-ethoxycarbonyl-thiourea, and N-(2-(cyanopentylureido)-phenyl)-N''-ethoxycarbonyl-thiourea.
 3. A method of combating fungi which comprises applying to said fungi or their habitat a fungicidally effective amount of a ureidophenyl thiourea of the formula:
 4. The method of claim 3 wherein the compound is N-(2-(phenylureido)-phenyl)-N''-ethoxycarbonyl-thiourea of the formula
 5. The method of claim 3 wherein the compound is N-(2-(benzylureido)-phenyl)-N''-ethoxycarbonyl-thiourea of the formula
 6. The method of claim 3 wherein the compound is N-(2-(methoxyethylureido)-phenyl)-N''-ethoxycarbonylthiourea of the formula
 7. The method of claim 3 wherein the compound is N-(2-(methylureido)-phenyl)-N''-ethoxycarbonyl-thiourea of the formula
 8. The method of claim 3 wherein the compound is N-(2-(dimethylaminoureido)-phenyl)-N''-ethoxycarbonylthiourea of the formula
 9. The method of claim 3 wherein the compound is N-(2-(cyanopentylureido)-phenyl)-N''-ethoxycarbonyl-thiourea of the formula 